Course

Unit 1

Gaseous state

Review of empirical gas laws. Kinetic theory of gases, ideal gas equation, Maxwell distribution of energy and velocities, collision parameters. Relation between mean free path and coefficient of viscosity. van der Waals equation, other state equations, law of corresponding states, liquefaction, Andrews curves, critical parameters, methods for liquefaction. Determination of molecular mass by limiting density method, critical phenomena, critical constants and their determination.

Unit 2

Thermodynamics – I

Thermodynamic processes – reversible and irreversible, isothermal and adiabatic processes. State and path functions. Exact and inexact differentials, concept of heat and work. First law of thermodynamics. Relation between Cp and Cv. Calculation of w, q, dE and dH for expansion of ideal and real gases under isothermal and adiabatic conditions of reversible and irreversible processes.
Thermochemistry – Enthalpy change of a reaction and different enthalpy changes – relation between enthalpy of reaction at constant volume and at constant pressure. Temperature dependence of heat of reaction – Kirchhoff’s equation. Bond energy and its calculation from thermochemical data – integral and differential heats.

Unit 3

Thermodynamics-II

Second law of thermodynamics – different statements of the law, Carnot’s cycle and efficiency of heat engine, Carnot’s theorem. Thermodynamic scale of temperature – concept of entropy – definition and physical significance of entropy – entropy as a function of P, V and T. Entropy changes during phase changes, entropy of mixing. Entropy criterion for spontaneous and equilibrium processes in isolated system, Gibb’s free energy (G) and Helmholtz free energy (A) – variation of A and G with P, V and T – Gibb’s – Helmholtz equation and its applications. Thermodynamic equation of state – Maxwell’s relations.

Unit 4

Thermodynamics – III

Third law of thermodynamics – need for third law, calculation of absolute entropy, unattainability of absolute zero, thermodynamic systems of variable composition. Fugacity functions, partial molar quantities, thermodynamics of ideal solutions, real solutions and regular solutions, dilute solutions of nonelectrolytes, Henry’s law, Raoult’s law, Gibbs-Duhem equations, Gibbs-Duhem-Margules equations, and activity and standard states of non-electrolytes.

Unit 5

Chemical Kinetics

Molecularity and order of a reaction, rate law expression and rate constant. First, second, third and zero order reactions, pseudo-first order reactions (pseudo-unimolecular reactions). Complex, parallel, chain, opposing and consecutive reactions. Equilibrium and steady state approximations – mechanism of these reactions. Effect of temperature on reaction rates – Arrhenius equation and its derivation, activation energy, characteristics of activated complex. Theories of reaction rates – collision theory – derivation of rate constant of bimolecular gases reaction – failure of collision theory – Lindemann’s theory of unimolecular reaction. Theory of absolute reaction rates – derivation of rate for a bimolecular reaction. Eyring equation – significance of entropy and free energy of activation.

1. Atkins, P., Atkins, P.W. and de Paula, J., 2006. Atkins’ physical chemistry. Oxford university press.
2. Gilbert William Castellan. 1983. Physical Chemistry, Addison Wesley; 3rd revised edition.
3. Ira Levin, ‘Physical Chemistry’, 6th edition, Tata Mcgraw-Hill Education, 2011.
4. Samuel Glasstone, Textbook of Physical Chemistry, Macmillan; 2nd edition.
5. Keith J Laidler, Chemical Kinetics, Pearson Publications, Third edition, 2003.
6. James E House, Principles of Chemical Kinetics, Second Edition, Academic Press, 2007.
7. Silbey, Alberty and Bawendi, Physical Chemistry, Fourth Edition, John Wiley and Sons.